KR102252723B1 - Surface-modified inorganic nitride, composition, thermally conductive material, device with thermally conductive layer - Google Patents

Abstract

An object of the present invention is to provide a surface-modified inorganic nitride excellent in dispersibility. Another object of the present invention is to provide a composition containing the surface-modified inorganic nitride, a thermally conductive material, and a device with a thermally conductive layer.
The surface-modified inorganic nitride of the present invention includes an inorganic nitride and a compound represented by the following general formula (I) adsorbed on the surface of the inorganic nitride.

Description

Surface-modified inorganic nitride, composition, thermally conductive material, device with thermally conductive layer

The present invention relates to a surface-modified inorganic nitride, a composition, a thermally conductive material, and a device with a thermally conductive layer.

In order to expand the application range of inorganic nitride, a method of modifying the surface of the inorganic nitride has been proposed.

For example, in the example of Patent Document 1, a method of treating the surface of aluminum nitride particles with 4-biphenylcarboxylic acid or 4-biphenylmethanol is disclosed.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-236376

On the other hand, when an inorganic nitride is mixed with an organic substance such as a resin binder, further improvement of the affinity of the inorganic nitride to the organic substance is required. For example, when an inorganic nitride such as boron nitride is mixed with an organic substance and used as a heat conductive material, from the viewpoint of further improvement in thermal conductivity, improvement in the dispersibility of the inorganic nitride in the organic substance is desired. In order to improve the dispersibility of the inorganic nitride, it is necessary to modify the surface of the inorganic nitride.

The present inventors prepared a surface-modified inorganic nitride in which the surface of boron nitride was treated with 4-biphenylcarboxylic acid or 4-biphenylmethanol with reference to Patent Document 1, and the surface-modified inorganic nitride was mixed with an organic substance to provide a thermal conductive material. Was prepared and the dispersibility of the surface-modified inorganic nitride in an organic substance was evaluated, and it was confirmed that the dispersibility was insufficient and further improvement was required.

Therefore, the present invention makes it a subject to provide a surface-modified inorganic nitride excellent in dispersibility.

Moreover, it is an object of the present invention to provide a composition containing the surface-modified inorganic nitride, a thermally conductive material, and a device with a thermally conductive layer.

The present inventors, as a result of earnestly examining in order to achieve the above object, found that the above object can be solved by using an inorganic nitride surface-treated with a compound represented by the general formula (I), and the present invention was completed.

That is, it has been found that the above object can be achieved by the following configuration.

[1] A surface-modified inorganic nitride comprising an inorganic nitride and a compound represented by the following general formula (I) adsorbed on the surface of the inorganic nitride.

[2] The surface-modified inorganic nitride according to [1], wherein X is a hydroxyl group, a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a phosphinic acid group, a sulfonic acid group, or a thiol group.

[3] The surface-modified inorganic nitride according to [1] or [2], wherein Y is an aromatic hydrocarbon ring group.

[4] The surface-modified inorganic nitride according to [3], wherein Y is a polycyclic aromatic hydrocarbon ring group containing three or more benzene rings.

[5] The surface-modified inorganic nitride according to [4], wherein Y is a pyrene cyclic group.

[6] The surface-modified inorganic nitride according to any one of [1] to [5], wherein the inorganic nitride is at least one selected from the group consisting of boron nitride and aluminum nitride.

[7] The surface-modified inorganic nitride according to [6], wherein the inorganic nitride is boron nitride.

[8] A composition comprising the surface-modified inorganic nitride according to any one of [1] to [7] and a polymerizable monomer.

[9] The composition according to [8], wherein the polymerizable monomer has a group selected from the group consisting of an acryloyl group, a methacryloyl group, an oxiranyl group, an oxetanyl group, and a vinyl group.

[10] The composition according to [8] or [9], wherein the polymerizable monomer or cured product thereof exhibits liquid crystallinity.

[11] The composition according to any one of [8] to [10], which is used to form a thermally conductive material.

[12] A thermally conductive material containing the surface-modified inorganic nitride according to any one of [1] to [7].

[13] The thermally conductive material according to [12], which is in the form of a sheet.

[14] The thermally conductive material according to [12] or [13], which is used for a heat dissipation sheet.

[15] A device with a heat conductive layer, comprising a device and a heat conductive layer comprising the heat conductive material according to any one of [12] to [14] disposed on the device.

ADVANTAGE OF THE INVENTION According to this invention, the surface-modified inorganic nitride excellent in dispersibility can be provided.

Further, according to the present invention, a composition containing the surface-modified inorganic nitride, a thermally conductive material, and a device with a thermally conductive layer can be provided.

1 shows the ultraviolet and visible absorption spectrum of a solution containing compound C-2 before and after boron nitride is added.
Fig. 2 shows an ultraviolet and visible absorption spectrum of a solution containing Compound C-3 before and after boron nitride is added.
Fig. 3 shows an ultraviolet and visible absorption spectrum of a solution containing Compound C-8 before and after boron nitride is added.
Fig. 4 shows the ultraviolet and visible absorption spectrum of a solution containing Compound C-15 before and after boron nitride is added.
Fig. 5 shows the ultraviolet and visible absorption spectrum of a solution containing Compound C-28 before and after boron nitride is added.

Hereinafter, the surface-modified inorganic nitride, the composition, the thermally conductive material, and the device with a thermally conductive layer of the present invention will be described in detail.

Although the description of the constitutional requirements described below may be made based on a representative embodiment of the present invention, the present invention is not limited to such an embodiment.

In addition, in this specification, the numerical range shown using "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value.

In this specification, the description of "(meth)acryloyl group" represents the meaning of "any one or both of an acryloyl group and a methacryloyl group".

In the present specification, the oxiranyl group is a functional group also called an epoxy group, and for example, a group in which two adjacent carbon atoms of a saturated hydrocarbon ring group are bonded by an oxo group (-O-) to form an oxylane ring is also oxy. I include it in the column diary.

In the present specification, the acid anhydride group may be a substituent obtained by excluding any hydrogen atom from an acid anhydride such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride.

In the present specification, "surface-modified inorganic nitride" means an inorganic nitride surface-modified with a compound represented by General Formula (I) described later (hereinafter, also referred to as "specific compound").

In the present specification, "surface modification" means a state in which a specific compound described later is adsorbed on at least a part of the surface of the inorganic nitride. The form of adsorption is not particularly limited, but it is preferably in a bonded state. In addition, the surface modification also includes a state in which an organic group (for example, a cationic group) obtained by desorbing a part of a specific compound is bonded to the surface of the inorganic nitride. The bond may be any bond such as a covalent bond, a coordination bond, an ionic bond, a hydrogen bond, a Van der Waals bond, and a metal bond. The surface modification may be made so as to form a monomolecular film on at least a part of the surface of the inorganic nitride.

In addition, in this specification, the surface modification may be only a part of the surface of the inorganic nitride or may be the whole.

In the present specification, the type of the substituent, the position of the substituent, and the number of the substituents in the case of "you may have a substituent" are not particularly limited. The number of substituents may be, for example, 1, 2, 3 or more. Examples of the substituent include a monovalent nonmetallic group excluding a hydrogen atom, and for example, it can be selected from the following substituent group T.

Substituent group T: halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, thiol group, alkylthio group, arylthio group, alkyldithio group, aryldithio group , Amino group, N-alkylamino group, N,N-dialkylamino group, N-arylamino group, N,N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarba Moyloxy group, N-arylcarbamoyloxy group, N,N-dialkylcarbamoyloxy group, N,N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acyl Thio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkyl ureido group, N',N'-dialkyl ureido group, N'-aryl ureido group, N',N '-Diaryl ureido group, N'-alkyl-N'-aryl ureido group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl Ureido group, N',N'-dialkyl-N-alkyl ureido group, N',N'-dialkyl-N-aryl ureido group, N'-aryl-N-alkyl ureido group, N'-aryl-N -Aryl ureido group, N',N'-diaryl-N-alkyl ureido group, N',N'-diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkyl ureido group , N'-alkyl-N'-aryl-N-aryl ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group , N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxy group and its conjugated base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group , N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-aryl carbamoyl group, N,N-diarylcarbamoyl group, N-alkyl-N-aryl carbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N,N -Dialkylsulfinamoyl group, N-arylsulfinamoyl group, N,N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, Sulfamoyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N -Acylsulfamoyl group and its conjugated base group, N-alkylsulfonylsulfamoyl group (-SO _{2 NHSO 2} (alkyl)) and its conjugated base group, N-arylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ ( aryl)) and its conjugated base group, N-alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonylcarbamoyl group (-CONHSO ₂ (aryl)) and its conjugated Base group, alkoxysilyl group (-Si(Oalkyl) ₃ ), aryloxysilyl group (-Si(Oaryl) ₃ ), hydroxysilyl group (-Si(OH) ₃ ) and its conjugated base group, phosphono group ( -PO ₃ H ₂ ) and its conjugated base group, a dialkylphosphono group (-PO ₃ (alkyl) ₂ ), a diarylphosphono group (-PO ₃ (aryl) ₂ ), an alkylarylphosphono group (-PO ₃ (alkyl)(aryl)), a monoalkylphosphono group (-PO ₃ H(alkyl)) and its conjugated base group, a monoarylphosphono group (-PO ₃ H(aryl)) and its conjugated base group, phos Phonooxy group (-OPO ₃ H ₂ ) and its conjugated base group, dialkylphosphonooxy group (-OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylaryl Phosphonooxy group (-OPO ₃ (alkyl)(aryl)), monoalkylphosphonooxy group (-OPO ₃ H(alkyl)) and its conjugated base group, monoarylphosphonooxy group (-OPO ₃ H(aryl) )) and its conjugated base group, cyano group, nitro group, aryl group, alkyl group, heterocyclic group, oxiranyl group, alkenyl group and alkyneyl group.

Moreover, if possible, these substituents may be bonded to each other or with the group being substituted to form a ring.

[Surface Modified Inorganic Nitride]

The surface-modified inorganic nitride of the present invention includes an inorganic nitride and a compound (specific compound) represented by general formula (I) described later adsorbed on the surface of the inorganic nitride. In other words, the surface-modified inorganic nitride of the present invention is a surface-modified inorganic nitride obtained by modifying the surface of an inorganic nitride with a specific compound described later.

In the surface-modified inorganic nitride of the present invention, a compound (specific compound) represented by General Formula (I) described later is used as the surface-modifying agent of the inorganic nitride.

As a characteristic point of a specific compound, Y as an aromatic hydrocarbon ring group or an aromatic heterocyclic group is a group having X as a hydrogen bonding group as a substituent (a group represented by *-L ¹ -X in General Formula (I)), and an adsorbent group. The point which each has one or more groups having Z (group represented by *-L ^{2 -Z in General Formula (I)) is mentioned.}

In the specific compound, due to the presence of the hydrogen bonding group, a plurality of specific compounds are liable to be connected by hydrogen bonding interactions. As a result, it is thought that the above-described specific compounds are connected to each other to form a planar structure having a plurality of aromatic hydrocarbon cyclic groups or aromatic heterocyclic groups (corresponding to Y), and is likely to be adsorbed on the surface of the inorganic nitride. Moreover, especially when the inorganic nitride is boron nitride, it has confirmed that the adsorption property is more excellent.

The surface-modified inorganic nitride formed by modifying the surface of the inorganic nitride by the above mechanism with a specific compound is excellent in dispersibility. As a result, the material containing the surface-modified inorganic nitride is presumed to be excellent in thermal conductivity because it is well dispersed and present in the material without uneven distribution of the surface-modified inorganic nitride. In particular, when the specific compound has a polymerizable group, the cured product obtained from the composition containing the surface-modified inorganic nitride and the polymerizable monomer is likely to form a conductive path between the surface-modified inorganic nitrides through the polymerizable monomer. It is thought that the thermal conductivity is improved more than that.

Moreover, when a specific compound has a condensed ring structure in a molecule|numerator, it is thought that the surface-modified inorganic nitride obtained also has a function of aligning a polymerizable monomer. As a result, in particular, when the polymerizable monomer or its cured product exhibits liquid crystallinity, the polymerizable monomer or its cured product is oriented (vertically aligned) on the surface of the surface-modified inorganic nitride, and the liquid crystal component aligned between the surface-modified inorganic nitrides is It is assumed that the intervening form is formed, the thermal conductivity between the surface-modified inorganic nitrides is further improved, and as a result, the thermal conductivity of the entire material is further improved.

Hereinafter, the components contained in the surface-modified inorganic nitride will be described in detail, and thereafter, a method for producing the surface-modified inorganic nitride and the use thereof will be described in detail.

<Inorganic Nitride>

The kind of inorganic nitride is not particularly limited.

Examples of inorganic nitrides include boron nitride (BN), carbon nitride (C ₃ N ₄ ), silicon nitride (Si ₃ N ₄ ), gallium nitride (GaN), indium nitride (InN), aluminum nitride (AlN), chromium nitride ( Cr ₂ N), copper nitride (Cu ₃ N), iron nitride (Fe ₄ N or Fe ₃ N), lanthanum nitride (LaN), lithium nitride (Li ₃ N), magnesium nitride (Mg ₃ N ₂ ), nitride Molybdenum (Mo ₂ N), niobium nitride (NbN), tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (W ₂ N, WN ₂ , or WN), yttrium nitride (YN), and Zirconium nitride (ZrN), etc. are mentioned.

The above inorganic nitrides may be used alone, or may be used in combination of a plurality of them.

The inorganic nitride preferably contains at least one selected from the group consisting of a boron atom, an aluminum atom, and a silicon atom from the viewpoint of more excellent thermal conductivity of the surface-modified inorganic nitride obtained. More specifically, the inorganic nitride is preferably at least one selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride, more preferably at least one selected from the group consisting of boron nitride and aluminum nitride, and more preferably nitride. Boron is particularly preferred.

The shape of the inorganic nitride is not particularly limited, and may be in the form of particles, films, or plates. In the case of a particulate form, for example, it may be a fine particle shape, a spherical shape, a cube shape, a spindle shape, a scale shape, an agglomerate shape, or an irregular shape.

The size of the inorganic nitride is not particularly limited, but from the viewpoint of more excellent dispersibility of the surface-modified inorganic nitride, the average particle diameter of the inorganic nitride is preferably 500 μm or less, more preferably 300 μm or less, and more preferably 200 μm or less. The lower limit is not particularly limited, but from the viewpoint of handling properties, 10 nm or more is preferable, and 100 nm or more is more preferable.

As a method of measuring the average particle diameter, 100 inorganic nitrides are randomly selected using an electron microscope, and the particle diameters (longer diameters) of each inorganic nitride are measured, and they are calculated by arithmetic average. Moreover, when using a commercial item, you may use a catalog value.

<Compound represented by general formula (I)>

The compound (specific compound) represented by the general formula (I) is a component adsorbed on the surface of the inorganic nitride as described above. Hereinafter, a specific compound will be described.

[Formula 1]

In General Formula (I), m and n each independently represent an integer of 1 or more. The upper limit of m and n is not particularly limited, but is, for example, 10 or less, respectively.

In general formula (I), X is a hydroxyl group (-OH), a carboxylic acid group (-COOH), a phosphonic acid group (-PO(OH) ₂ ), a phosphoric acid group (-OP(=O)(OH) ₂ ), and a phosphonic acid group. It represents a finic acid group (-HPO(OH)), a sulfonic acid group (-SO ₃ H), a thiol group (-SH), or an amino group.

It does not specifically limit as said amino group, Any of primary, secondary, and tertiary may be sufficient. Specifically, -N(R ^A ) ₂ (R ^A is each independently a hydrogen atom or an alkyl group (including both linear, branched and cyclic). The number of carbon atoms in the alkyl group is, for example, It is 1 to 10, preferably 1 to 6, and more preferably 1 to 3. In addition, the alkyl group may further have a substituent (eg, a group exemplified by the substituent group T). Can be lifted.

The X is preferably a hydroxyl group, a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a phosphinic acid group, a sulfonic acid group, or a thiol group from the viewpoint of more excellent dispersibility.

In General Formula (I), when a plurality of X is present, a plurality of X may be the same or different, respectively.

Said Y represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

As the aromatic hydrocarbon ring group, any of a monocyclic aromatic hydrocarbon ring group and a polycyclic aromatic hydrocarbon ring group may be used.

Although it does not specifically limit as a monocyclic aromatic hydrocarbon ring which comprises a monocyclic aromatic hydrocarbon ring group, For example, a 5-10-membered ring is mentioned, and a 5-membered or 6-membered ring is preferable. Examples of the monocyclic aromatic hydrocarbon ring include a cyclopentadienyl ring and a benzene ring.

The polycyclic aromatic hydrocarbon ring is not particularly limited as long as it has two or more monocyclic aromatic hydrocarbon rings, but a condensed ring containing two or more benzene rings is more preferable, and a condensed ring containing three or more benzene rings is More preferable. In addition, the upper limit of the number of monocyclic aromatic hydrocarbon rings contained in the condensed ring is not particularly limited, but is often 10 or less, for example.

As a polycyclic aromatic hydrocarbon ring, specifically, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, pyrene, chrysene , Tetracene, pleiaden, picene, perylene, pentafen, pentacene, tetraphenylene, hexafen, and triphenylene. In view of the more excellent effects of the present invention, among the above, a condensed ring containing two or more benzene rings is more preferable, a condensed ring containing three or more benzene rings is more preferable, and pyrene or perylene is particularly preferable, Pyrene is most preferred.

As the aromatic heterocyclic group, any of a monocyclic aromatic heterocyclic group and a polycyclic aromatic heterocyclic group may be used. In addition, the polycyclic aromatic heterocycle constituting the polycyclic aromatic heterocyclic group refers to a condensed ring composed of two or more monocyclic aromatic heterocycles, and one or more monocyclic aromatic heterocycles and one or more monocyclic aromatic hydrocarbon rings. It means a condensed ring formed.

Although it does not specifically limit as a monocyclic aromatic heterocycle, For example, a 5-membered to 10-membered ring is mentioned, and a 5-membered or 6-membered ring is preferable. As a hetero atom contained in a monocyclic aromatic heterocycle, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example.

Examples of the monocyclic aromatic heterocycle include a thiophene ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring.

Specific examples of the polycyclic aromatic heterocycle include a benzimidazole ring, an indole ring, a quinoline ring, and a quinoxaline ring.

Since Y is more excellent in dispersibility, an aromatic hydrocarbon ring group is preferable, and a polycyclic aromatic hydrocarbon ring group is more preferable.

Further, the aromatic hydrocarbon group or aromatic heterocyclic group represented by Y may have a substituent (for example, a group exemplified by the substituent group T).

Z is an aldehyde group (-CHO), succinic acid imide group, onium group, halogenated alkyl group, halogen atom (F atom, Cl atom, Br atom, and I atom), nitrile group (-CN), nitrate _{Ro group (-NO 2} ), acryloyl group (-COCH ₂ =CH ₂ ), methacryloyl group (-COCH(CH ₃ )=CH ₂ ), oxetanyl group, vinyl group (-CH=CH ₂ ), Alkainyl group (a group excluding one hydrogen atom from alkyne. For example, an ethyneyl group and a propa-2-yn-1-yl group are included), or a group having a maleimide group or a carbonate group ( for example, an alkyl carbonate group: represents a (-O-CO-OR ^B to be described later for R ^B.)).

The succinic acid imide group, oxetanyl group, and maleimide group each represent a group formed by excluding one hydrogen atom at an arbitrary position from a compound represented by the following formula.

[Formula 2]

In addition, the said onium group means a group which has an onium salt structure. The onium salt is a compound generated by coordinating a compound having an electron pair not involved in a chemical bond with another cationic compound by the electron pair. Usually, the onium salt contains a cation and an anion.

Although it does not specifically limit as an onium salt structure, For example, an ammonium salt structure, a pyridinium salt structure, an imidazolium salt structure, a pyrrolidinium salt structure, a piperidinium salt structure, a triethylenediamine salt structure, a phosphonium salt structure, a sulfonium salt structure , And a thiopyryllium salt structure. In addition, the kind of anion used as a counter is not particularly limited, and a known anion is used. The valence of the anion is also not particularly limited, for example, 1 to 3 valent, and 1 to 2 valent is preferable.

As the onium group, among others, a group having an ammonium salt structure represented by the following general formula (A1) is preferable.

[Formula 3]

In General Formula (A1), R ^1A to R ^3A each independently represent a hydrogen atom or an alkyl group (linear, branched, and cyclic all are included). The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 3. M ^- represents an anion. * Represents a bonding position. In addition, the alkyl group may further have a substituent (for example, a group exemplified by the substituent group T).

Although it does not specifically limit as said halogenated alkyl group, For example, what substituted one or more halogen atoms in a C1-C10 alkyl group is mentioned. The number of carbon atoms in the alkyl group (including both linear, branched and cyclic) is preferably 1 to 6, and more preferably 1 to 3. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, or a bromine atom is preferable. In addition, the halogenated alkyl group may further have a substituent (for example, a group exemplified by the substituent group T).

The group having a carbonate group is not particularly limited as long as it has a carbonate group, and examples thereof include an alkyl carbonate group (-O-CO-OR ^B ).

The ^{number of carbon atoms in the alkyl group represented by R B} is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 3. In addition, the alkyl group may further have a substituent (for example, a group exemplified by the substituent group T).

When a plurality of Z is present in the general formula (I), the plurality of Z may be the same or different, respectively.

The L ¹ and L ² are each independently a single bond or from the group consisting of -O-, -CO-, -S-, -CS-, -NR ¹¹ -, -N=N-, and a divalent hydrocarbon group. Any one selected or a combination of two or more divalent linking groups is shown. The divalent hydrocarbon group may further have a substituent (for example, a group exemplified by the substituent group T).

Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group (eg -CH=CH-), an alkynylene group (eg -C≡C-), and an arylene group (eg phenylene group). Can be mentioned. As the alkylene group, any of linear, branched and cyclic may be used. Moreover, 1-10 are preferable, as for the carbon number, 1-6 are more preferable, and 1-4 are more preferable.

R ¹¹ represents a hydrogen atom or an alkyl group (either linear, branched or cyclic. As for carbon number, 1 to 6 are preferable, and 1 to 3 are more preferable).

As the L ¹ and L ² , since the dispersibility is more excellent, each independently, a single bond, -AL-, -CO-, -CO-O-, -O-CO-, -AL-O-,- O-AL-, -AL-CO-O-, -CO-O-AL-, -AL-O-CO-, -O-CO-AL, -AL-O-AL-, -AL-NR ^11- CO-, -AL-CO-NR ¹¹ -, -NR ¹¹ -CO-AL-, -CO-NR ¹¹ -AL-, or -AR-O-AL-O- is preferable, and a single bond is more preferable. . Said AL represents an alkylene group having 1 to 10 carbon atoms (the number of carbons is preferably 1 to 6, more preferably 1 to 3). Moreover, said AR represents an arylene group. The alkylene group and the arylene group may further have a substituent (for example, a group exemplified by the substituent group T).

In addition, in General Formula (I), L<^{1> which} exists in plural may be the same or different, respectively. ^{Moreover, L 2 which} exists in a plurality may be the same or different, respectively.

The molecular weight of the specific compound is, for example, 100 or more, and preferably 150 or more, more preferably 280 or more, and 3,000 or less from the viewpoint of solubility, from the viewpoint of more excellent dispersibility of the surface-modified inorganic nitride. And 2,000 or less is more preferable.

Specific examples of specific compounds are shown below, but the present invention is not limited thereto. In addition, in the following examples, "Me" represents a methyl group, and "Et" represents an ethyl group.

[Formula 4]

[Formula 5]

[Formula 6]

<Method for producing surface-modified inorganic nitride>

The method for producing the surface-modified inorganic nitride is not particularly limited, and examples thereof include a method having a step of bringing the inorganic nitride into contact with a specific compound.

The contact of the inorganic nitride and the specific compound is carried out, for example, by stirring the solution containing the inorganic nitride and the specific compound.

The kind of the solvent of the solution is not particularly limited, but an organic solvent is preferable. As an organic solvent, ethyl acetate, methyl ethyl ketone, dichloromethane, and tetrahydrofuran are mentioned, for example.

The solution may contain other components such as a polymerizable monomer described later. In this case, the obtained mixture can also be used as a composition mentioned later.

The mixing ratio of the inorganic nitride and the specific compound may be determined in consideration of the structure and surface area of the inorganic nitride and the molecular structure such as the aspect ratio of the molecule of the specific compound.

The stirring conditions (stirring rotation speed, temperature conditions) are not particularly limited.

<Surface Modified Inorganic Nitride>

In the surface-modified inorganic nitride, the specific compound has surface-modified the inorganic nitride. It is preferable that the specific compound forms a bond such as an inorganic nitride and a hydrogen bond to achieve surface modification.

The shape of the surface-modified inorganic nitride is not particularly limited, and may be a particle shape, a film shape, or a plate shape.

The mass ratio of the specific compound and the inorganic nitride in the surface-modified inorganic nitride (mass of the specific compound/mass of the inorganic nitride) is not particularly limited, but since the dispersibility of the surface-modified inorganic nitride is more excellent, the mass ratio is 0.0001 to 0.5 is preferable and 0.0005 to 0.1 are more preferable.

In the surface-modified inorganic nitride, a specific compound may be adsorbed on the surface of the inorganic nitride, and other surface-modifying agents may be adsorbed on the surface of the inorganic nitride. That is, the surface-modified inorganic nitride may contain an inorganic nitride, a specific compound adsorbed on the surface of the inorganic nitride, and other surface-modifying agents.

〔Composition〕

The surface-modified inorganic nitride has improved dispersibility in various materials. Using this, the surface-modified inorganic nitride can be mixed with other materials and applied to various uses as a composition.

The content of the surface-modified inorganic nitride in the composition is not particularly limited, and an optimal content is appropriately selected according to the use of the composition. The content of the surface-modified inorganic nitride is, for example, 0.01 to 95% by mass with respect to the total solid content in the composition. In particular, since the properties of the surface-modified inorganic nitride are more exhibited, the content of the surface-modified inorganic nitride is With respect to the total solid content, 20 to 95% by mass is preferable, 30 to 90% by mass is more preferable, and 40 to 85% by mass is still more preferable.

The composition may contain one type of surface-modified inorganic nitride, or may contain two or more types.

As described above, the composition may contain materials other than the surface-modified inorganic nitride, and examples thereof include a polymerizable monomer, a curing agent, a curing accelerator, and a polymerization initiator.

Hereinafter, various components will be described in detail.

<Polymerizable monomer>

The polymerizable monomer is a compound cured by a predetermined treatment such as heat or light.

The polymerizable monomer has a polymerizable group.

The kind of the polymerizable group is not particularly limited, and a known polymerizable group is mentioned. From the viewpoint of reactivity, a functional group capable of an addition polymerization reaction is preferred, and a polymerizable ethylenically unsaturated group or a ring polymerizable group is more preferred. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an oxiranyl group, a vinyl group, a maleimide group, a styryl group, an allyl group, and an oxetanyl group. In addition, the hydrogen atom in each of the groups may be substituted with another substituent such as a halogen atom. The polymerizable group is preferably a group selected from the group consisting of an acryloyl group, a methacryloyl group, an oxiranyl group, an oxetanyl group, and a vinyl group from the viewpoint of reactivity.

In addition, the number of polymerizable groups contained in the polymerizable monomer is not particularly limited, but from the viewpoint of more excellent heat resistance of the cured product obtained by curing the composition, it is preferably two or more, and more preferably three or more. Although the upper limit is not particularly limited, it is often 8 or less.

The kind of polymerizable monomer is not particularly limited, and a known polymerizable monomer can be used. For example, the epoxy resin monomer and acrylic resin monomer described in paragraph 0028 of JP-A-4118691, the epoxy compound described in paragraphs 0006-0011 of JP 2008-013759, and the paragraph of JP 2013-227451 A The epoxy resin mixture described in 0032 to 0100, etc. are mentioned.

Further, a bisphenol A diglycidyl ether monomer, a bisphenol F diglycidyl ether monomer, and the like can also be used.

The content of the polymerizable monomer in the composition is not particularly limited, and an optimum content is appropriately selected according to the use of the composition. Among them, the content of the polymerizable monomer is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, and still more preferably 15 to 60% by mass with respect to the total solid content in the composition.

The composition may contain one type of polymerizable monomer, or may contain two or more types.

It is preferable that a polymerizable monomer shows liquid crystallinity. That is, it is preferable that the polymerizable monomer is a liquid crystal compound. In other words, it is preferable that it is a liquid crystal compound having a polymerizable group.

Moreover, it is also preferable that a cured product of a polymerizable monomer exhibits liquid crystallinity. In addition, the cured product of a polymerizable monomer means a cured product obtained by curing the polymerizable monomer itself, and the surface-modified inorganic nitride described above is not included. Moreover, when obtaining the said hardened|cured material, you may use a hardening|curing agent mentioned later as needed.

As described above, it is preferable that a polymerizable monomer or a cured product thereof exhibits liquid crystallinity. That is, it is preferable that a polymerizable monomer or its cured product is a liquid crystal component.

The polymerizable monomer may be any of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound. That is, the polymerizable monomer may be any of a rod-like liquid crystal compound having a polymerizable group and a disk-like liquid crystal compound having a polymerizable group.

Hereinafter, the rod-shaped liquid crystal compound and the disk-shaped liquid crystal compound will be described in detail.

(Stick liquid crystal compound)

Examples of rod-shaped liquid crystal compounds include azomethanes, azoxyls, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and cyano-substituted phenylpyrimidines. , Alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolans, and alkenylcyclohexylbenzonitriles. In addition to the low-molecular liquid crystal compounds as described above, a high-molecular liquid crystal compound can also be used. The polymeric liquid crystal compound is a polymer compound obtained by polymerizing a rod-like liquid crystal compound having a low molecular weight reactive group.

As a preferable rod-shaped liquid crystal compound, a rod-shaped liquid crystal compound represented by the following general formula (XXI) is mentioned.

General Formula (XXI): Q ¹ -L ¹¹¹ -A ¹¹¹ -L ¹¹³ -ML ¹¹⁴ -A ¹¹² -L ¹¹² -Q ²

In the formula, Q ¹ and Q ² are each independently a polymerizable group, and L ¹¹¹ , L ¹¹² , L ¹¹³ , and L ¹¹⁴ each independently represent a single bond or a divalent linking group. A ¹¹¹ and A ¹¹² each independently represent a C1-C20 divalent linking group (spacer group). M represents a mesogen group.

In addition, the definition of the polymerizable group is as described above.

Examples of the divalent linking group represented by L ¹¹¹ , L ¹¹² , L ¹¹³ , and L ^{114 include -O-, -S-, -CO-, -NR 112} -, -CO-O-, -O-CO-O-, -CO-NR ¹¹² -, -NR ¹¹² -CO-, -O-CO-, -CH ₂ -O-, -O-CH ₂ -, -O-CO-NR ¹¹² -, -NR ¹¹² -CO-O It is preferably a divalent linking group selected from the group consisting of -, and -NR ¹¹² -CO-NR ^{112 -.} R ¹¹² is a C 1 to C 7 alkyl group or a hydrogen atom.

A ¹¹¹ and A ¹¹² represent a C1-C20 divalent linking group. Especially, a C1-C12 alkylene group, an alkenylene group, or an alkynylene group is preferable, and a C1-C12 alkylene group is more preferable.

The divalent linking group is preferably linear, and may contain an oxygen atom or a sulfur atom that is not adjacent. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, or a bromine atom), a cyano group, a methyl group, and an ethyl group.

As a mesogenic group represented by M, a well-known mesogenic group is mentioned. Among them, a group represented by the following general formula (XXII) is preferable.

General Formula (XXII): -(W ¹ -L ¹¹⁵ ) _n -W ^2-

In the formula, W ¹ and W ² each independently represent a divalent cyclic alkylene group, a divalent cyclic alkenylene group, an arylene group, or a divalent heterocyclic group. L ¹¹⁵ represents a single bond or a divalent connecting group. n represents 1, 2 or 3.

Examples of W ¹ and W ² include 1,4-cyclohexendiyl, 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridin-2, 5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene -1,5-diyl, thiophene-2,5-diyl, and pyridazine-3,6-diyl are mentioned. In the case of 1,4-cyclohexanediyl, either of the structural isomers of the trans form and the cis form may be used, or a mixture of any ratio may be used. Among them, a trans chain is preferable.

W ¹ and W ² may each have a substituent. Examples of the substituent include groups exemplified by the aforementioned substituent group T, and more specifically, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, and a carbon number of 1 ~10 alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), C1-C10 alkoxy group (e.g., methoxy group, ethoxy group, etc.), C1-C10 acyl group (e.g. , Formyl group, acetyl group, etc.), C1-C10 alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), C1-C10 acyloxy group (e.g., acetyloxy group) , Propionyloxy group, etc.), a nitro group, a trifluoromethyl group, and a difluoromethyl group.

Examples of the divalent linking group represented by L ¹¹⁵ include specific examples of the divalent linking group represented by L ¹¹¹ to L ¹¹⁴ described above, for example, -CO-O-, -O-CO-, -CH ₂ -O -, and -O-CH ₂ -are mentioned.

What is preferable as a basic skeleton of a mesogenic group represented by the said general formula (XXII) is illustrated below. These substituents may be substituted with the above substituents.

[Formula 7]

[Formula 8]

In addition, the compound represented by general formula (XXI) can be synthesized by referring to the method described in Japanese Laid-Open Patent Publication No. Hei 11-513019 (WO97/000600).

The rod-shaped liquid crystal compound may be a monomer having a mesogen group described in JP 11-323162 A and JP 4118691 A.

(Disc liquid crystal compound)

The disk-like liquid crystal compound has a disk-like structure at least partially. The disk-like structure has at least an aromatic ring. For this reason, the disk-like liquid crystal compound can form a columnar structure by forming a stacking structure by π-π interaction between molecules.

As a disk-like structure, specifically, Angew. Chem. Int. Ed. 2012, 51, 7990-7993 or the triphenylene structure described in Japanese Patent Laid-Open No. 7-306317, and the trisubstituted benzene structure described in Japanese Laid-Open Patent Publication No. 2007-002220 and 2010-244038, etc. Can be lifted.

Among them, by using a disk-like liquid crystal compound as a polymerizable monomer, a thermally conductive material exhibiting high thermal conductivity can be obtained. The reason for this is that while the rod-shaped liquid crystal compound can only conduct heat in a linear (one-dimensional) direction, the disk-shaped liquid crystal compound can conduct heat in a planar (two-dimensional) direction in the normal direction. It is thought that this is improved.

Moreover, by using a disk-like liquid crystal compound, the heat resistance of the cured product of a composition improves.

It is preferable that the disk-like liquid crystal compound has three or more polymerizable groups. A cured product of a composition containing a disk-like liquid crystal compound having three or more polymerizable groups tends to have a high glass transition temperature and high heat resistance. Compared with the rod-shaped liquid crystal compound, the disk-shaped liquid crystal compound tends to have three or more polymerizable groups without affecting the properties of the mesogenic moiety. It is preferable that it is 8 or less, and, as for the number of polymeric groups which a disk-like liquid crystal compound has, it is more preferable that it is 6 or less.

As a disk-like liquid crystal compound, a compound represented by the following general formula (XI) or a compound represented by general formula (XII) is preferable.

[Formula 9]

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent *-X ¹¹ -L ¹¹ -P ¹¹ or *-X ¹² -Y ¹² , * is triphenyl Represents a bonding position with a ren ring, and at least two of ^{R 11} , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ^{16 are *-X 11} -L ¹¹ -P ¹¹ , and X ¹¹ and X ¹² are each Independently, a single bond, -O-, -C(=O)-, -OC(=O)-, -OC(=O)O-, -OC(=O)NH-, -OC(=O) S-, -C(=O)O-, -C(=O)NH-, -C(=O)S-, -NHC(=O)-, -NHC(=O)O-, -NHC( =O)NH-, -NHC(=O)S-, -S-, -SC(=O)-, -SC(=O)O-, -SC(=O)NH-, or -SC(= Represents O)S-, L ¹¹ represents a divalent linking group or single bond, P ¹¹ represents a polymerizable group, Y ¹² represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Or in a C1-C20 linear, branched, or cyclic alkyl group, one or two or more methylene groups -O-, -S-, -NH-, -N(CH ₃ )-, -C(= It represents a group substituted with O)-, -OC(=O)-, or -C(=O)O-.

It is preferable that three or more of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ^{16 are *-X 11} -L ¹¹ -P ^11. Among them, it is more preferable ^{that any one or more of R 11} and R ¹² , any one or more of R ¹³ and R ¹⁴ , and any one or more of R ¹⁵ and R ¹⁶ are *-X ¹¹ -L ¹¹ -P ¹¹ And, it is more preferable that ^{R 11} , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are all *-X ¹¹ -L ¹¹ -P ^{11 , and R 11} , R ¹² , R ¹³ , R ¹⁴ , It is particularly preferred that R ¹⁵ and R ¹⁶ are all the same *-X ¹¹ -L ¹¹ -P ^11.

As X ¹¹ and X ¹² , each independently, -O-, -OC(=O)-, -OC(=O)O-, -OC(=O)NH-, -C(=O)O-, -C(=O)NH-, -NHC(=O)-, or -NHC(=O)O- is preferred, and -OC(=O)-, -C(=O)O-, -OC( =O)NH-, or -C(=O)NH- is more preferable, and -C(=O)O- is more preferable.

L ¹¹ represents a divalent linking group or a single bond connecting ^{X 11} and P ^11. As a divalent linking group, -O-, -OC(=O)-, -C(=O)O-, C1-C10 (preferably C1-C8, more preferably C1-C6) alkyl An arylene group having 6 to 20 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms), or a group formed of a combination thereof.

Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

Examples of the arylene group having 6 to 20 carbon atoms include 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 1, 5-naphthylene group, and anthracenylene group. And a 1,4-phenylene group is preferable.

Each of the alkylene group and the arylene group may have a substituent. Examples of the substituent include groups exemplified by the above-described substituent group T. As for the number of substituents, it is preferable that it is 1-3, and it is more preferable that it is one. The substitution position of the substituent is not particularly limited. As a substituent, a halogen atom or a C1-C3 alkyl group is preferable, and a methyl group is more preferable. It is also preferable that the alkylene group and the arylene group are unsubstituted. In particular, it is preferable that the alkylene group is unsubstituted.

P ¹¹ represents a polymerizable group. The definition of the polymerizable group is as described above.

It is preferable that P ¹¹ is an acryloyl group, a methacryloyl group, or an oxiranyl group.

Moreover, when P ¹¹ is a hydroxy group, it is preferable that ^{L 11} contains an arylene group, and this arylene group ^{is bonded to P 11.}

Y ¹² is one or two or more methylene groups in a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms- O-, -S-, -NH-, -N(CH ₃ )-, -C(=O)-, -OC(=O)-, or a group substituted with -C(=O)O-.

Y ¹² is a C1-C20 linear, branched, or cyclic alkyl group, or a C1-C20 linear, branched, or cyclic alkyl group, wherein one or two or more methylene groups are -O-,- In the case of a group substituted with S-, -NH-, -N(CH ₃ )-, -C(=O)-, -OC(=O)-, or -C(=O)O-, substituted with a halogen atom It may be.

As a C1-C20 linear or branched alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group , Isopentyl group, neopentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, linear or branched heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dode A practical machine is mentioned.

The number of carbon atoms in the cyclic alkyl group is preferably 3 or more, more preferably 5 or more, more preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

As Y ¹² , a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an alkylene oxide group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 12 carbon atoms, or An ethylene oxide group or a propylene oxide group having 1 to 20 carbon atoms is more preferable.

For specific examples of the compound represented by the general formula (XI), paragraphs 0028 to 0036 of JP-A-7-281028, JP-A-7-306317A, and paragraphs 0016- of JP-A-2005-156822. Reference can be made to those described in 0018, paragraphs 0067 to 0072 of JP 2006-301614 A, and pages 330 to 333 of the Liquid Crystal Handbook (published by Maruzen Co., Ltd. in 2012).

[Formula 10]

In the formula, A ² , A ³ , and A ⁴ each independently represent -CH= or -N=, and R ¹⁷ , R ¹⁸ , and R ¹⁹ are each independently *-X ²¹¹ -(Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ²¹ or *-X ²¹¹ -(Z ²² -X ²²² ) _n22 -Y ²² represents, * represents the bonding position with the central ring, 2 of R ¹⁷ , R ¹⁸ , and R ¹⁹ At least one is *-X ²¹¹ -(Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ²¹ , and X ²¹¹ , X ²¹² , and X ²²² are each independently a single bond, -O-, -C(=O )-, -OC(=O)-, -OC(=O)O-, -OC(=O)NH-, -OC(=O)S-, -C(=O)O-, -C( =O)NH-, -C(=O)S-, -NHC(=O)-, -NHC(=O)O-, -NHC(=O)NH-, -NHC(=O)S-, -S-, -SC(=O)-, -SC(=O)O-, -SC(=O)NH-, or -SC(=O)S-, Z ²¹ and Z ²² are each independently , the 5-membered ring or 6-membered ring aromatic group, or a 5-membered ring, or represents a non-aromatic 6-membered ring of, L ²¹ is, represents a divalent connecting group or a single bond linking the X ²¹² and P ^21, P ²¹ is a polymerizable group And Y ²² is a hydrogen atom, one or two or more methylene groups in a C 1 to C 20 linear, branched or cyclic alkyl group, or a C 1 to C 20 linear, branched or cyclic alkyl group -O-, -S-, -NH-, -N(CH ₃ )-, -C(=O)-, -OC(=O)-, or -C(=O)O- , n ₂₁ and n ₂₂ each independently represent an integer of 0 to 3, and when n ₂₁ and n ₂₂ are 2 or more, a plurality of Z ²¹ -X ²¹² and Z ²² -X ²²² may be the same or different. .

It is preferable that all of R ¹⁷ , R ¹⁸ , and R ¹⁹ are *-X ²¹¹ -(Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ^21. It is more preferable that R ¹⁷ , R ¹⁸ , and R ¹⁹ are all the same *-X ²¹¹ -(Z ²¹ -X ²¹² ) _n21 -L ²¹ -P ^21.

As X ²¹¹ , X ²¹² , and X ²²² , a single bond or -OC(=O)- is preferable.

Z ²¹ and Z ²² each independently represent a 5- or 6-membered aromatic group, or a 5- or 6-membered non-aromatic group, such as 1,4-phenylene group, 1,3-phenylene group, and 2 A heterocyclic group, etc. are mentioned.

The aromatic group and the non-aromatic group may have a substituent. Examples of the substituent include groups exemplified by the above-described substituent group T. One or two substituents are preferred, and one substituent is more preferred. The substitution position of the substituent is not particularly limited. As the substituent, a halogen atom or a methyl group is preferable. The halogen atom is preferably a chlorine atom or a fluorine atom. It is also preferable that the aromatic group and the non-aromatic group are unsubstituted.

As a divalent heterocycle, the following heterocycles are mentioned, for example.

[Formula 11]

In the formula, * ^{represents a site binding to X 211} , ** represents a site binding to X ²¹² (or X ²²² ); A ⁴¹ and A ⁴² each independently represent a metain group or a nitrogen atom; X ⁴ represents an oxygen atom, a sulfur atom, a methylene group, or an imino group.

It is preferable that at least one of A ⁴¹ and A ⁴² is a nitrogen atom, and it is more preferable that both are nitrogen atoms. Moreover, ^{it is preferable that X 4} is an oxygen atom.

L ²¹ represents a divalent linking group or a single bond connecting ^{X 212} and P ²¹ , and is synonymous with ^{L 11 in General Formula (XI).} As L ²¹ , -O-, -OC(=O)-, -C(=O)O-, an alkylene group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms) Or a group consisting of a combination thereof is preferred.

P ²¹ represents a polymerizable group. The definition of the polymerizable group is as described above.

It is preferable that P ²¹ is an acryloyl group, a methacryloyl group, or an oxiranyl group.

Each of Y ²² is independently a hydrogen atom, a C 1 to C 20 linear, branched or cyclic alkyl group, or a C 1 to C 20 linear, branched or cyclic alkyl group having 1 or 2 or more Methylene group -O-, -S-, -NH-, -N(CH ₃ )-, -C(=O)-, -OC(=O)-, or -C(=O)O- ^{It represents a group, and is synonymous with Y 12} in General Formula (XI), and the preferable range is also the same.

Each of n ₂₁ and n ₂₂ independently represents an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably 2 or 3.

For details and specific examples of the compound represented by General Formula (XII), description of paragraphs 0013 to 0077 of JP 2010-244038A can be referred to, and the contents are incorporated herein by reference.

From the viewpoint of enhancing the stacking by reducing the electron density and making it easier to form a columnar aggregate, the compound represented by the general formula (XI) or (XII) is preferably a compound having a hydrogen bonding functional group.

As a hydrogen bonding functional group, -OC(=O)NH-, -C(=O)NH-, -NHC(=O)-, -NHC(=O)O-, -NHC(=O)NH-, -NHC(=O)S-, and SC(=O)NH-, etc. are mentioned.

The following compounds are mentioned as an especially preferable specific example as a compound represented by General formula (XI) and a compound represented by General formula (XII).

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

The compound represented by general formula (XI) is described in JP-A-7-306317A, JP-A-7-281028A, JP-A-2005-156822, and JP-A-2006-301614. It can be synthesized according to the method.

The compound represented by the general formula (XII) can be synthesized according to the method described in JP 2010-244038 A, JP 2006-076992 A, and JP 2007-002220 A.

<Other ingredients>

(Hardener)

The composition may further contain a curing agent.

The type of the curing agent is not particularly limited, and any compound capable of curing the above-described polymerizable monomer may be used. The curing agent is preferably a compound having a functional group selected from the group consisting of a hydroxy group, an amino group, a thiol group, an isocyanate group, a carboxy group, a (meth)acryloyl group, and an anhydrous carboxylic acid group, and a hydroxy group, It is more preferable that it is a compound which has a functional group selected from the group consisting of a (meth)acryloyl group, an amino group, and a thiol group.

It is preferable that the curing agent contains two or more of the said functional groups, and it is more preferable that it contains two or three.

Examples of the curing agent include amine curing agents, phenol curing agents, guanidine curing agents, imidazole curing agents, naphthol curing agents, acrylic curing agents, acid anhydride curing agents, active ester curing agents, benzoxazine curing agents, and cyanate esters. System hardening agents, etc. are mentioned. Among them, an acrylic curing agent, a phenolic curing agent, or an amine curing agent is preferable.

The content of the curing agent in the composition is not particularly limited, but is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass with respect to the total solid content in the composition.

(Hardening accelerator)

The composition may further contain a curing accelerator.

The kind of curing accelerator is not limited, for example, triphenylphosphine, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, 1-benzyl-2-methylimidazole, and Japanese Laid-Open Patent Publication. What was described in paragraph 0052 of 2012-067225 is mentioned.

The content of the curing accelerator in the composition is not particularly limited, but is preferably 0.1 to 20% by mass with respect to the total solid content in the composition.

(Polymerization initiator)

The composition may further contain a polymerization initiator.

In particular, when a specific compound or polymerizable monomer has a (meth)acryloyl group, the composition comprises a polymerization initiator described in paragraph 0062 of Japanese Laid-Open Patent Publication 2010-125782 and paragraph 0054 of Japanese Laid-Open Patent Publication 2015-052710. It is desirable.

The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 50% by mass based on the total solid content in the composition.

(menstruum)

The composition may further contain a solvent.

The kind of solvent is not particularly limited, and it is preferably an organic solvent. As an organic solvent, ethyl acetate, methyl ethyl ketone, dichloromethane, tetrahydrofuran, etc. are mentioned, for example.

<Production method of the composition>

The method for producing the composition is not particularly limited, and a known method can be employed, and for example, it can be produced by mixing the above-described various components (such as surface-modified inorganic nitride and polymerizable monomer) by a known method. When mixing, various components may be mixed collectively or may be mixed sequentially.

In addition, as described above, when producing a surface-modified inorganic nitride, an inorganic nitride, a specific compound, and other additives may be collectively mixed to prepare a composition.

<How to cure the composition>

The curing method of the composition is not particularly limited, and an optimal method is appropriately selected according to the kind of the polymerizable monomer. The curing method may be, for example, a thermosetting reaction or a photocuring reaction, and a thermosetting reaction is preferable.

The heating temperature during the thermosetting reaction is not particularly limited. For example, what is necessary is just to select suitably in the range of 50-200 degreeC. Moreover, when performing a thermosetting reaction, you may perform heat treatment at different temperatures over multiple times.

In addition, it is preferable to perform curing reaction with respect to the composition made into a sheet shape. Specifically, for example, a composition may be applied and the resulting coating film may be subjected to a curing reaction. In that case, you may perform press working.

Moreover, the curing reaction may be a semi-curing reaction. That is, the obtained cured product may be in a so-called B-stage state (semi-cured state).

After arranging the above-described semi-cured cured product in contact with a device or the like, by further curing it by heating or the like, the adhesion between the layer containing the heat-conductive material as the cured product and the device is further improved.

<use>

The surface-modified inorganic nitride and the composition can be applied to various uses. For example, it can be applied to various fields such as pigments, catalysts, electrode materials, semiconductor materials, thermally conductive materials, and lubricants. That is, the material containing the surface-modified inorganic nitride can be applied to various uses. In addition, the shape of the material containing the surface-modified inorganic nitride is not particularly limited, and may be, for example, a sheet shape.

Among them, it is preferable to use the surface-modified inorganic nitride and the composition to form a thermally conductive material or a lubricant.

Hereinafter, this suitable use will be described in detail.

(Heat conductive material)

The thermally conductive material of the present invention contains a surface-modified inorganic nitride.

Components other than the surface-modified inorganic nitride may be contained in the thermally conductive material, and for example, a binder may be mentioned. Further, examples of the binder include a binder formed by curing the above-described polymerizable monomer.

The thermally conductive material can be produced by curing the above-described composition. That is, the composition can be used to form a thermally conductive material. In addition, for the production of a thermally conductive material including a curing reaction, reference can be made to "high thermally conductive composite material" (CMC Schuppan, by Takezawa Yoshitaka).

In addition, the said heat-conducting material just needs to contain a surface-modified inorganic nitride, and its manufacturing method is not limited to the aspect using the said composition.

The thermally conductive material is a material having excellent thermal conductivity, and can be used as a heat dissipating material such as a heat dissipating sheet. For example, it can be used for heat dissipation of various devices such as power semiconductor devices. More specifically, by arranging a heat conductive layer containing the heat conductive material on the device to fabricate a device with a heat conductive layer, heat generated from the device can be efficiently radiated from the heat conductive layer.

The shape of the heat conductive material is not particularly limited, and may be molded into various shapes depending on the application. Typically, it is preferable that the heat conductive material is in the form of a sheet.

Further, the thermally conductive material may be in a completely cured state or may be in a semi-cured state (the above-described B-stage state). As described above, if it is a heat conductive material in a semi-cured state, it is possible to form a heat conductive layer having excellent adhesion on the device by performing heat treatment after being disposed on the device.

(slush)

The surface-modified inorganic nitride can be suitably used for producing a lubricant. That is, as the use of the surface-modified inorganic nitride, a lubricant containing the surface-modified inorganic nitride is exemplified.

The lubricant can be produced by mixing a grease (low molecular weight monomer, polymer resin) or the like with a surface-modified inorganic nitride. As the grease, a known material can be used.

When producing a lubricant, boron nitride is preferably mentioned as the inorganic nitride in the surface-modified inorganic nitride. This is because it is known that boron nitride itself exhibits lubricity in a high temperature region.

Example

Hereinafter, the present invention will be described in more detail based on examples. Materials, usage, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

〔Establishment of the experimental system〕

Alizarin is a well-known compound that binds with zinc oxide to modify the surface of zinc oxide (Japanese Patent Publication No. 5479175). 12 mg of Alizarin (manufactured by Wako Junyaku Corporation, catalog number 015-01151) was dissolved in 300 mL of methyl ethyl ketone, and the absorbance at a wavelength of 427 nm was measured using the visible absorption spectrum of this solution (measuring device: UV-3100PC manufactured by Shimadzu Seisakusho). did. Further, to this solution (25 mL), zinc oxide fine particles prepared separately (made by Wako Junyaku Corporation, 264-00365) were added, and the mixture was stirred lightly. After about 5 minutes, the supernatant of the obtained solution was filtered and filtered using a 0.45 micron filter (Minisart RC15 manufactured by Sartorius). About the obtained filtrate, the absorbance was measured in the same manner as above. As a result, with respect to the absorbance of the solution before the addition of the zinc oxide fine particles, the absorbance of the solution after the addition of the zinc oxide fine particles was 27.6%. From the obtained results, it was found that by performing the above-described comparison of absorbance, the presence or absence of surface modification of the inorganic nitride of the compound and its degree can be determined from the decrease in absorbance.

(Adsorption test for inorganic nitride)

A solution was obtained by dissolving the following compound C-2 (10 mg) in an acetonitrile group (100 mL) and diluting it by 1/10. The ultraviolet-visible absorption spectrum (measuring apparatus: Shimadzu Corporation UV-3100PC) of the obtained solution was measured, and the absorbance X at the maximum absorption wavelength was calculated|required.

Next, boron nitride "SGPS" (0.5 g) manufactured by Denka Corporation was added to the solution (20 mL), followed by stirring for several seconds. After stirring, the supernatant of the obtained solution was filtered and filtered. Using the obtained filtrate, the ultraviolet and visible absorption spectrum (measuring apparatus: Shimadzu Corporation UV-3100PC) of the filtrate was measured in the same manner as described above, and the absorbance Y at the maximum absorption wavelength was determined. The results of the ultraviolet and visible absorption spectrum are shown in Fig. 1.

Subsequently, the ratio of the absorbance Y at the maximum absorption wavelength of the filtrate obtained by adding boron nitride to the absorbance X at the maximum absorption wavelength of the solution before adding the boron nitride (remaining rate (%)) was calculated. The smaller the residual ratio (%) is, the better the adsorption to boron nitride is. Table 1 shows the results.

In addition, instead of C-2, each compound shown in Table 1 described later was used, and the residual ratio (%) of the absorbance after addition of boron nitride was calculated according to the same procedure as described above. Each result is put together in Table 1 mentioned later, and is shown.

In addition, the results of the ultraviolet and visible absorption spectrum in the case of using the following compounds are shown in Figs. 2 to 5, respectively.

[Formula 22]

[Table 1]

As can be seen from the results of Table 1, when each of the compounds shown in Table 1 was used, a decrease in absorbance was observed in all cases. From this result, it was confirmed that each compound shown in Table 1 was adsorbed on the surface of boron nitride. In addition, among the compounds C-1 to 16 and C-18 to C to 35 used in Examples to be described later, a decrease in absorbance was also observed when a compound other than the compound shown in Table 1 was used. From this result, it was confirmed that among the compounds C-1 to 16 and C-18 to C to 35 used in Examples described later, compounds other than the compounds shown in Table 1 were also adsorbed on the surface of boron nitride.

〔Preparation and evaluation of the composition〕

<Various ingredients>

Below, various components used in Examples and Comparative Examples are shown.

(Polymerizable monomer)

As a polymerizable monomer, a compound represented by the following A-1 to A-8 was used.

A-1: Mixture of bisphenol F diglycidyl ether resin and bisphenol A diglycidyl ether resin, epoxy equivalent: 165.7 g/eq, total chlorine: 0.008 mass%, viscosity: 2,340 mPa·s, Shinnittetsu sumi Made by Keen Chemical Company.

[Formula 23]

A-5: "TMPT" (trimethylolpropane triacrylate, Shinnakamura Chemical Co., Ltd. product).

A-6: "OXT-121" (multifunctional oxetane, manufactured by Toa Kosei Co., Ltd.).

[Formula 24]

(additive)

As an additive, a compound represented by the following B-1 to B-3 was used.

[Formula 25]

B-3: "KAYAHARD GPH-65" (manufactured by Nippon Kayaku Co., Ltd.)

(solvent)

As the solvent, MEK (methyl ethyl ketone) was used.

(Polymerization initiator)

As the polymerization initiator, VAm-110 (oil-soluble azo polymerization initiator, manufactured by Wako Junyaku Corporation) was used.

(Inorganic Nitride)

As the inorganic nitride, the following were used.

SGPS (boron nitride, average particle diameter 12μm, manufactured by Denka Corporation)

S-30 (Aluminum nitride, average particle diameter 35 μm, manufactured by MARUWA)

(Surface Modifier)

As a surface modifier, a compound represented by the following C-1 to C-16 and C-18 to C-35 was used.

[Formula 26]

[Formula 27]

[Formula 28]

(Surface modifier for comparison)

As a surface modifier for comparison, a compound represented by the following D-1 to D-4 was used.

[Formula 29]

<Example 1>

After mixing the various components shown in Table 2 below in the order of a polymerizable monomer, MEK (methyl ethyl ketone), an additive, a surface modifier (a compound represented by the general formula (I)), and a polymerization initiator, an inorganic nitride was added. did. Composition 1 was obtained by treating the obtained mixture for 5 minutes with a rotating revolution mixer (manufactured by THINKY, Awatori Rentaro ARE-310). In addition, the final solid content of the composition 1 was adjusted to MEK so that the solid content concentration (described in the "solvent" column) shown in Table 2 might be obtained.

Next, using an applicator, the composition 1 was applied so that the film thickness was about 600 μm on the release surface of the polyester film (NP-100A, film thickness 100 μm), and then the coating film 1 was left to stand in the air for 1 hour. Got it.

Next, the coating surface of the coating film 1 was covered with another polyester film, and the coating film was cured by processing by vacuum hot pressing (hot plate temperature 130°C, vacuum degree ≤ 1 kPa, pressure 12 MPa, treatment time 5 hours) to obtain a resin sheet. The polyester films on both sides of the resin sheet were peeled off to obtain a thermally conductive sheet 1 having an average film thickness shown in Table 1 (in Example 1, an average film thickness of 350 μm).

(evaluation)

About the obtained thermally conductive sheet 1, the following evaluation was performed.

[1] Dispersion evaluation

The dispersibility evaluation was performed using the thermally conductive sheet 1. Specifically, the film thickness of the thermally conductive sheet 1 was measured at five arbitrary positions, the standard deviation was calculated for the measurement deviation, and evaluated according to the following criteria. When the standard deviation is small (in other words, when the deviation in film thickness is small), it indicates that the surface-modified inorganic nitride is well dispersed. On the other hand, when the standard deviation is large (in other words, when the film thickness is large), it means that agglomeration or the like occurs in the cured product, resulting in surface irregularities, that is, the dispersibility of the surface-modified inorganic nitride is inferior. .

The film thickness measurement was performed using "I-Phase Mobile 1u" manufactured by I-Phase Corporation.

(Evaluation standard)

"A": standard deviation less than 5

"B": standard deviation of 5 or more and less than 10

"C": standard deviation of 10 or more and less than 30

"D": standard deviation of 30 or more

Table 2 shows the results.

[2] Thermal conductivity evaluation

Thermal conductivity evaluation was performed using the thermal conductivity sheet 1. The measurement of the thermal conductivity was performed by the following method, and the thermal conductivity was evaluated according to the following criteria.

·Measurement of thermal conductivity (W/mK)

(1) The thermal diffusivity of the thermally conductive sheet 1 in the thickness direction was measured using "Eye Phase Mobile 1u" manufactured by Eye Phase.

(2) The specific gravity of the thermally conductive sheet 1 was measured using a balance "XS204" (using "solid specific gravity measurement kit") manufactured by METTLER TOLEDO.

(3) Using "DSC320/6200" manufactured by Seiko Instruments, the specific heat of the thermally conductive sheet 1 at 25°C was determined using DSC7 software under a temperature rising condition of 10°C/min.

(4) The thermal conductivity of the thermally conductive sheet 1 was calculated by multiplying the obtained thermal diffusivity by the specific gravity and specific heat.

(Evaluation standard)

"A": 15W/m·K or more

"B": 12W/m·K or more and less than 15 W/m·K

"C": 9W/m·K or more and 12 W/m·K or less

"D": less than 9W/m·K

Table 2 shows the results.

<Examples 2 to 45, Comparative Examples 1 to 4>

By the same procedure as in Example 1, each composition of Examples and Comparative Examples shown in Table 2 below was obtained. In addition, the final solid content of the composition was adjusted to MEK so that the solid content concentration (described in the “solvent” column) shown in Table 2 might be obtained.

Moreover, from each of the obtained compositions, thermally conductive sheets 2 to 45 and comparative thermally conductive sheets 1 to 4 were produced, and the same evaluation test as in Example 1 was performed. Table 2 shows the results.

In Table 2, (numerical value) described in each component column means the content (mass%) of each component with respect to the total solid content in the composition.

In addition, the "film thickness (μm)" described in Table 2 means the average film thickness of the thermally conductive sheet.

In Table 2, the curing accelerator A used in Example 44 is triphenylphosphine.

[Table 2]

[Table 3]

[Table 4]

As shown in the above table, it was confirmed that the thermal conductivity was more excellent when the surface-modified inorganic nitride of the present invention was used. This improvement in thermal conductivity is because the dispersibility of the surface-modified inorganic nitride in the sample is improved. That is, it was confirmed that the affinity between the surface-modified inorganic nitride and the organic material was improved.

Further, from the contrast between Example 15 and Example 33, it was confirmed that when boron nitride was used as the inorganic nitride, the dispersibility was more excellent.

In addition, from the comparison of Examples 1-45, in the general formula (I), when X has a hydroxyl group, a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a phosphinic acid group, a sulfonic acid group, or a thiol group, the dispersibility is more It was confirmed that there was a good tendency.

In addition, from the comparison of Examples 1 to 45, in the general formula (I), when Y is a polycyclic aromatic hydrocarbon ring group containing 3 or more benzene rings (preferably a pyrene ring group), the thermal conductivity is more It was confirmed to be improved.

In addition, from the comparison of Examples 39 to 43, when the polymerizable monomer has a group selected from the group consisting of an acryloyl group, a methacryloyl group, an oxiranyl group, an oxetanyl group, and a vinyl group, the thermal conductivity is further improved. It was confirmed to be.

Claims (15)

A surface-modified inorganic nitride comprising an inorganic nitride and a compound represented by the following general formula (I) adsorbed on the surface of the inorganic nitride.
[Formula 1]

In General Formula (I), X represents a hydroxyl group, a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a phosphinic acid group, a sulfonic acid group, a thiol group, or an amino group. Y represents an aromatic hydrocarbon cyclic group or an aromatic heterocyclic group. Z is an aldehyde group, a succinic acid imide group, an onium group, a halogenated alkyl group, a halogen atom, a nitrile group, an acryloyl group, a methacryloyl group, an oxetanyl group, a vinyl group, an alkyneyl group, or a maleimide group Or a group having a carbonate group. L ¹ and L ² are each independently a single bond or a group consisting of -O-, -CO-, -S-, -CS-, -NR ¹¹ -, -N=N-, and a divalent hydrocarbon group Any one selected from or a combination of two or more divalent linking groups is shown. R ¹¹ represents a hydrogen atom or an alkyl group. m and n each independently represent an integer of 1 or more.
In addition, in General Formula (I), when a plurality of X is present, the plurality of X may be the same or different, respectively. In addition, when a plurality of Z is present, the plurality of Z may be the same or different, respectively. In the case where the presence of a plurality of L ^1, L ¹ is present in plurality, it may be the same or each may be different. In addition, ^{when a plurality of L 2} is present, a plurality of L ² may be the same or different, respectively.
However, when X represents an amino group, Z represents a group other than a halogen atom. The method according to claim 1,
The surface-modified inorganic nitride wherein X is a hydroxyl group, a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a phosphinic acid group, a sulfonic acid group, or a thiol group. The method according to claim 1 or 2,
The surface-modified inorganic nitride wherein Y is an aromatic hydrocarbon ring group. The method of claim 3,
The surface-modified inorganic nitride wherein Y is a polycyclic aromatic hydrocarbon ring group containing three or more benzene rings. The method of claim 4,
The surface-modified inorganic nitride wherein Y is a pyrene ring group. The method according to claim 1 or 2,
The surface-modified inorganic nitride, wherein the inorganic nitride is at least one selected from the group consisting of boron nitride and aluminum nitride. The method of claim 6,
The surface-modified inorganic nitride wherein the inorganic nitride is boron nitride. A composition comprising the surface-modified inorganic nitride according to claim 1 or 2 and a polymerizable monomer. The method of claim 8,
The composition wherein the polymerizable monomer has a group selected from the group consisting of an acryloyl group, a methacryloyl group, an oxiranyl group, an oxetanyl group, and a vinyl group. The method of claim 8,
A composition in which the polymerizable monomer or cured product thereof exhibits liquid crystallinity. The method of claim 8,
A composition used to form a thermally conductive material. A thermally conductive material containing the surface-modified inorganic nitride according to claim 1 or 2. The method of claim 12,
Sheet-shaped heat-conducting material. The method of claim 12,
Thermally conductive material used for heat dissipation sheet. A device with a thermally conductive layer, comprising a device and a thermally conductive layer comprising the thermally conductive material according to claim 12 disposed on the device.

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